FR2620055A1 - CHEMICAL METHOD FOR DESTRUCTION OF HALOGENIC ORGANIC PRODUCTS - Google Patents
CHEMICAL METHOD FOR DESTRUCTION OF HALOGENIC ORGANIC PRODUCTS Download PDFInfo
- Publication number
- FR2620055A1 FR2620055A1 FR8712248A FR8712248A FR2620055A1 FR 2620055 A1 FR2620055 A1 FR 2620055A1 FR 8712248 A FR8712248 A FR 8712248A FR 8712248 A FR8712248 A FR 8712248A FR 2620055 A1 FR2620055 A1 FR 2620055A1
- Authority
- FR
- France
- Prior art keywords
- products
- alcoholate
- organic products
- destruction
- halogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000006378 damage Effects 0.000 title abstract description 7
- 239000000126 substance Substances 0.000 title description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 150000003071 polychlorinated biphenyls Chemical class 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 7
- -1 alkali metal alkoxide Chemical class 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000002013 dioxins Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 150000004826 dibenzofurans Chemical class 0.000 claims description 2
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical class C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims 1
- 150000004961 triphenylmethanes Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 40
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 150000004074 biphenyls Chemical class 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- NDRKXFLZSRHAJE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br NDRKXFLZSRHAJE-UHFFFAOYSA-N 0.000 description 1
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- WZTJFRVXSHGGEF-UHFFFAOYSA-N 1-chloro-4-(2-phenylethyl)benzene Chemical compound C1=CC(Cl)=CC=C1CCC1=CC=CC=C1 WZTJFRVXSHGGEF-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/34—Dehalogenation using reactive chemical agents able to degrade
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
Landscapes
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fire-Extinguishing Compositions (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Insulating Materials (AREA)
- Processing Of Solid Wastes (AREA)
- Polyesters Or Polycarbonates (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
Description
PROCEDE CHIMIQUE DE DESTRUCTION DE PRODUITS ORGANIQUES HALOGENESCHEMICAL METHOD FOR DESTRUCTION OF HALOGENIC ORGANIC PRODUCTS
La présente invention concerne un procédé chimique de destruction de produits organiques halogénés et plus particulièrement des produits aromatiques chlorés tels que par exemple les PCB (polychlorobiphényles) éventuellement mélangés à des produits organiques non chlorés. -On a déjà proposé dans l'art antérieur d'enlever les PCB contenus dans des huiles diélectriques de transformateurs ou des huiles de lubrification par extraction avec du méthanol (brevet US 4387018). Le méthanol est ensuite séparé des PCB par distillation puis recyclé. Ce The present invention relates to a chemical process for destroying halogenated organic products and more particularly chlorinated aromatic products such as for example PCBs (polychlorinated biphenyls) optionally mixed with non-chlorinated organic products. It has already been proposed in the prior art to remove PCBs contained in dielectric oils from transformers or lubricating oils by extraction with methanol (US Pat. No. 4,388,708). The methanol is then separated from the PCBs by distillation and then recycled. This
procédé permet de réduire de 70 % la quantité de PCB. Le brevet euro- This process reduces the amount of PCB by 70%. The European patent
péen EP 99951 propose de traiter des produits semblables par le sodium en dispersion de particules supérieures à 10 Mm. La demande de brevet européen EP 107404 décrit le traitement d'une huile de transformateur contenant 652 ppm de PCB par des sels de sodium d'un polyéthylene glycol. Ces procédés ont l'inconvénient de nécessiter des séparations EP 99951 proposes to treat similar products with sodium in dispersion of particles greater than 10 μm. European patent application EP 107404 describes the treatment of a transformer oil containing 652 ppm of PCB with sodium salts of polyethylene glycol. These methods have the disadvantage of requiring separations
et des recyclages ou de manipuler du sodium. La demande de brevet. and retraining or handling sodium. The patent application.
européen EP 21294 décrit la destruction des dioxines en particulier des EP 21294 describes the destruction of dioxins, in particular
anisoles chlorés contenant 39,7 ppm de 2,3,7,8-tétrachlorodibenzo-p- chlorinated anisoles containing 39.7 ppm 2,3,7,8-tetrachlorodibenzo-p-
dioxine, en faisant réagir ces produits sous pression avec du méthylate ZO de sodium dans le méthanol à 160 C. De plus un article de Gyula Pfeifer et Terez Flora dans la revue hongroise MAGY. KEM. FOLYOIRAT 71 (8) , 343-6 (1965) explique que le méthylate de sodium peut commencer à se décomposer entre 120 et 140 C. On a maintenant trouvé un procédé dioxin, by reacting these products under pressure with sodium methoxide ZO in methanol at 160 C. In addition an article by Gyula Pfeifer and Terez Flora in the Hungarian magazine MAGY. KE M. FOLYOIRAT 71 (8), 343-6 (1965) explains that sodium methoxide can begin to decompose between 120 and 140 C. A process has now been found
beaucoup plus simple et très efficace. much simpler and very effective.
Z5 La présente invention concerne un procédé de destruction de produits organiques halogénés caractérisé en ce que: a) Ces produits sont mis en contact avec au moins un alcoolate de The present invention relates to a process for the destruction of halogenated organic products, characterized in that: a) These products are brought into contact with at least one alcoholate of
métal alcalin le temps nécessaire pour convertir les halogènes organi- alkali metal the time required to convert the organic halogens
ques en halogénures inorganiques,inorganic halides,
b) la quantité d'alcoolate est en excès par rapport à la stoechio- (b) the amount of alcoholate is in excess of the stoichiometric
métrie basée sur la quantité d'halogène, metrics based on the amount of halogen,
c) la température est supérieure à 220 C. c) the temperature is above 220 C.
L'invention s'intéresse à tous les produits halogénés mais plus The invention is concerned with all halogenated products but more
particulièrement aux produits contenant des carbones aryliques substi- particularly to products containing substituted aryl carbons
tués par du chlore et/ou du brome. Dans cette famille on trouve par exemple les dioxines chlorées ou bromées, les dibenzofurannes chlorés ou bromés, les (polychloro)biphényles, les (polybromo)biphényles, les (polybromo)diphényléthers, les (polychloro)diphényléthers. Ces produits peuvent être purs ou mélangés entre eux ou en mélange avec des produits organiques non halogénés, tels que des polyarylalcanes, des huiles minérales. Bien que l'invention permette la destruction de tout produit halogéné, elle est avantageusement mise en oeuvre pour des produits contenant moins de 1 % en poids d'halogène et de préférence moins de killed by chlorine and / or bromine. In this family are found for example chlorinated or brominated dioxins, chlorinated or brominated dibenzofurans, (polychloro) biphenyls, (polybromo) biphenyls, (polybromo) diphenyl ethers, (polychloro) diphenyl ethers. These products can be pure or mixed with each other or mixed with non-halogenated organic products, such as polyarylalkanes, mineral oils. Although the invention allows the destruction of any halogenated product, it is advantageously used for products containing less than 1% by weight of halogen and preferably less than
1000 ppm.1000 ppm.
Bien qu'on puisse utiliser tout alcoolate dérivé d'un monoalcool, Although it is possible to use any alcoholate derived from a monoalcohol,
d'un diol ou d'un triol et d'un métal alcalin et parmi eux les méthy- of a diol or a triol and an alkali metal and among them the methyl-
lates et alcoolate de glycol ou polyglycol, on utilise avantageusement le méthylate, l'éthylate, le propylate ou l'isopropylate de sodium, lithium ou potassium ou un mélange de ces produits et de préférence le and laurate glycol or polyglycol alcohol, is advantageously used the methylate, ethylate, propylate or isopropylate of sodium, lithium or potassium or a mixture of these products and preferably the
méthylate de sodium.sodium methoxide.
Avantageusement l'alcoolate est ajouté dans les produits halogénés ou le mélange contenant les produits halogénés. De préférence on utilise le méthylate de sodium en poudre. La stoechiométrie étant une fonction alcoolate par atome d'halogène à éliminer on utilise une quantité d'alcoolate en excès par rapport à cette stoechiométrie. On obtient une très bonne dehalogénation en utilisant un excès de 5 à 10 fois la stoechiométrie. Par exemple si un mélange contient des PCB en proportion de 100 ppm exprimés en chlore, on utilise une quantité de Advantageously, the alcoholate is added to the halogenated products or the mixture containing the halogenated products. Preferably sodium methoxide powder is used. Since the stoichiometry is an alcoholic function per halogen atom to be eliminated, an excess amount of alkoxide is used relative to this stoichiometry. A very good dehalogenation is obtained using an excess of 5 to 10 times the stoichiometry. For example, if a mixture contains PCBs in proportion of 100 ppm expressed in chlorine, a quantity of
méthylate de sodium de 0,14 %.sodium methoxide 0.14%.
On ne sortirait pas du cadre de l'invention en ajoutant avec l'alcoolate un autre produit pouvant transformer le chlore organique en chlorure inorganique comme par exemple le carbonate de sodium, ou un It would not be departing from the scope of the invention to add with the alkoxide another product which can convert organic chlorine into inorganic chloride, for example sodium carbonate, or
autre agent alcalin.other alkaline agent.
Avantageusement la mise en contact des produits organiques halogé- Advantageously, the contacting of the halogenated organic products
nés avec l'alcoolate est effectuée sous agitation par exemple dans un with the alcoholate is carried out with stirring for example in a
réacteur agité ou une colonne garnie, ou tout autre dispositif permet- agitated reactor or a packed column, or any other device
tant une agitation suffisante pour que l'alcoolate soit bien dispersé et soit au contact des produits halogénés le temps nécessaire à leur sufficient agitation for the alcoholate to be well dispersed and in contact with the halogenated products the time required for their
destruction. La réaction peut être effectuée en continu ou en discon- destruction. The reaction can be carried out continuously or in discon-
tinu. La cinétique de réaction augmente avec la température. On peut utiliser une température comprise entre 220 et 300 C, on préfère opérer tinu. The kinetics of reaction increases with temperature. It is possible to use a temperature of between 220 and 300 ° C., it is preferred to operate
entre 250 et 290 C. Selon les propriétés physiques des produits (ten- between 250 and 290 C. Depending on the physical properties of the products (
sion de vapeur) on opère à la pression atmosphérique ou sous pression plus élevée. La durée de réaction est fonction des quantités d'halogène steam is operated at atmospheric pressure or under higher pressure. The reaction time depends on the amounts of halogen
organique, de la température, de la quantité d'alcoolate, des condi- organic matter, the temperature, the amount of alcoholate, the conditions
tions d'agitation pour effectuer une bonne mise en contact des réac- stirring conditions to ensure good contact between the reaction
tifs; elle est habituellement comprise entre 30 minutes et 10 heures. L'invention est particulièrement utile pour détruire les produits halogénés aryliques contenus dans un mélange par exemple un liquide diélectrique non halogéné ou une huile minérale contenant des PCB. On applique à ce produit contenant les PCB ou d'autres produits chlorés le procédé de l'invention, puis on sépare par exemple par distillation les produits halogénés inorganiques des autres produits. On obtient ainsi tive; it is usually between 30 minutes and 10 hours. The invention is particularly useful for destroying aryl halogenated products contained in a mixture, for example a non-halogenated dielectric liquid or a mineral oil containing PCBs. The process of the invention is applied to this product containing the PCBs or other chlorinated products, and the inorganic halogenated products are, for example, separated from the other products by distillation. We obtain
une huile minérale, un diélectrique exempt de chlore organique. a mineral oil, a dielectric free of organic chlorine.
Pour être sûr de faire une déhalogénation la plus complète possi- To be sure to do the most complete dehalogenation possible
ble on utilise un excès d'alcoolate. Quand on traite un fluide diélec- an excess of alcoholate is used. When treating a dielectric fluid
trique qui contient quelques centaines de ppm de produits chlorés aromatiques à la fin de la réaction, on obtient le diélectrique, du chlorure NaCl, les produits de transformation des produits chlorés aromatiques, et le reste d'alcoolate non réagi. Il est très commode de distiller ce mélange pour récupérer le diélectrique pur ne contenant plus de chlore aromatique. Il est prudent quand l'alcoolate utilisé est du méthylate de sodium de ne pas dépasser des temps de séjour dans It contains a few hundred ppm of aromatic chlorinated products at the end of the reaction, the dielectric, NaCl chloride, the products of transformation of chlorinated aromatic products, and the unreacted alkoxide residue. It is very convenient to distil this mixture to recover pure dielectric no longer containing aromatic chlorine. It is prudent when the alcoholate used is sodium methoxide not to exceed residence times in
l'appareil à distiller de 12 heures à 295 C pour éviter une décomposi- distilling apparatus for 12 hours at 295 C to avoid decomposition
tion du méthylate.methylate.
Le procédé de la présente invention s'utilise aussi en complément d'un procédé au carbonate de sodium. Le carbonate de sodium est très The process of the present invention is also used in addition to a sodium carbonate process. Sodium carbonate is very
facile à manipuler mais ne permet d'enlever que les halogènes alipha- easy to handle but only allows the removal of aliphatic halogens
tiques ainsi que les halogènes aryliques les plus labiles. ticks as well as the most labile aryl halogens.
Le procédé de l'invention permet d'obtenir un produit avec une teneur en halogène arylique inférieure à 10 ppm. L'avantage de ce procédé est que, bien que s'appliquant à des produits ayant des atomes d'halogène peu réactifs, il ne nécessite pas l'emploi de solvants; C'est-à-dire qu'il suffit d'ajouter un alcoolate par exemple dans l'huile contenant les PCB sans avoir l'obligation d'ajouter, en plus de l'alcoolate, de l'alcool correspondant à l'alcoolate comme dans le The process of the invention makes it possible to obtain a product with an aryl halogen content of less than 10 ppm. The advantage of this method is that, while applying to products having low reactive halogen atoms, it does not require the use of solvents; That is to say that it is sufficient to add an alcoholate for example in the oil containing the PCBs without the obligation to add, in addition to the alcoholate, the alcohol corresponding to the alcoholate as in the
EP 21294. Ce procédé n'exige pas en fin de traitement, avant de récupé- EP 21294. This method does not require at the end of treatment, before recovering
rer les produits débarassés des halogènes aryliques, de séparation préalable de l'excès d'alcoolate, en particulier du méthylate de sodium. Un autre avantage du procédé est que les sous produits formés tels que le chlorure NaCl, les produits halogénés aryliques transformés par l'alcoolate et le reste d'alcoolate non réagi peuvent être détruits remove the aryl halogenated products, prior separation of the excess alcoholate, in particular sodium methoxide. Another advantage of the process is that the formed by-products such as NaCl chloride, the alkoxide-converted halogenated products and the unreacted alcoholate residue can be destroyed.
facilement par incinération sans générer des produits toxiques. easily by incineration without generating toxic products.
Les exemples suivants illustrent l'invention sans la limiter. The following examples illustrate the invention without limiting it.
EXEMPLE 1EXAMPLE 1
On prend 1000 g de dibenzyltoluène (DBT) contenant 300 ppm de chlore aromatique sous la forme de monochlorobenzyltoluène. Ce mélange 1000 g of dibenzyltoluene (DBT) containing 300 ppm of aromatic chlorine in the form of monochlorobenzyltoluene are taken. This mixture
est placé dans un réacteur muni d'une agitation rotative, d'un réfrigé- is placed in a reactor equipped with a rotary stirrer, a refrigerator
rant ascendant et d'un injecteur d'azote. Après balayage pendant 15 minutes par un courant d'azote à 100 C, on ajoute 1 % en poids (soit g) de méthylate de sodium. Le milieu est porté à reflux à 285 C, avec agitation et balayage d'azote pendant 3 heures. Le produit est ensuite distillé avec mise progressive du vide jusqu'à 2 mm de mercure de manière à ne pas dépasser 300 C dans le pied. Le distillat obtenu a rant and a nitrogen injector. After washing for 15 minutes with a stream of nitrogen at 100 ° C., 1% by weight (ie g) of sodium methoxide is added. The mixture is refluxed at 285 ° C., with stirring and nitrogen sweeping for 3 hours. The product is then distilled with progressive setting of the vacuum up to 2 mm of mercury so as not to exceed 300 C in the foot. The distillate obtained
une teneur.totale en chlore aromatique de 3 ppm. a total aromatic chlorine content of 3 ppm.
A titre de comparaison, en effectuant le traitement du même produit contenant les mêmes produits chlorés avec du carbonate de By way of comparison, by treating the same product containing the same chlorinated products with
sodium, on obtient un produit ayant une teneur totale en chlore aroma- sodium, a product having a total content of aromatic chlorine is obtained.
tique de l'ordre de 100 ppm.tick of the order of 100 ppm.
EXEMPLE 2EXAMPLE 2
On traite du DBT comme dans l'exemple 1 mais avec NaOC2H5, KOCH3, KOC2H5, NaOCH(CH3)2, dans les conditions de l'exemple 1. Les résultats DBT is treated as in Example 1 but with NaOC2H5, KOCH3, KOC2H5, NaOCH (CH3) 2 under the conditions of Example 1. The results
sont reportés sur le tableau.are shown on the chart.
EXEMPLE 3EXAMPLE 3
a) On traite du DBT contenant 1000 ppm de PCB pendant 3 heures à 280 C avec 1 % de méthylate de sodium. On obtient un produit contenant a) DBT containing 1000 ppm of PCB is treated for 3 hours at 280 ° C with 1% sodium methoxide. We obtain a product containing
moins de 15 ppm de chlore.less than 15 ppm of chlorine.
b) Identique à a) sauf que le DBT contient 1000 ppm de tétrachlo- (b) Same as (a) except that DBT contains 1000 ppm of tetrachloro-
robenzyltoluène.robenzyltoluène.
Les résultats sont reportés sur le tableau. The results are shown on the chart.
EXEMPLE 4EXAMPLE 4
a) On traite une huile minérale contenant 1000 ppm de PCB pendant 3 heures à 280 C avec 1 % de CH3ONa. On obtient un produit contenant a) A mineral oil containing 1000 ppm of PCB is treated for 3 hours at 280 ° C with 1% CH3ONa. We obtain a product containing
moins de 15 ppm d'halogène.less than 15 ppm halogen.
b) Identique à a) sauf que l'huile minérale contient 1000 ppm d'octabromobiphényle. *aeSua aTinq,p a!Tquenb el e auamei 'ainmolq ap amaoj snos amoiq ap mdd 9t9 ap uotaetTsTp ap npflsa al suep a2esoa (*) ageSnua alTitnqp gqTzuenb el e auamei ainiolqz ap auWoj snos aiolqz ap mdd 08g ap uoFIelltsip ap nptsgaal suep a2eso () S t i mdd l > i e ZNOHI Z () aluqdIqomoaqozDoop t mdd 0001 + alveiaum alTnH i mdd Si > i LNOHO % I i () salolqa 9 ai ap i ;;i; mdd 0001 + alaeaUTm alTnH i i i t alWIcWXai 0 i i úi i m dd çl > t eLO HD Z anooo i i i úi -eaigi ap mdd OOOl + OOl ig i i mdd Sl > eNO HD % I i (saaolqo <9) i i; j ap mdd 0001 + 001 úR i i i i i i mdd ú i ROHD(zH) % 'O i i çz mdd Sl > 0 H D 4 auanloi; i mdd Sl >; MoúD Z ç'0 i -lXzuaqoaotlqOUom ap uamoj; mdd ç > i eiNO HZ% I isnos aaolqo ap mdd oOg + lÉ i i i i z Maauxa i i i i i i i i i i ?TITSTP la i i i i gze1l iTnpoid atli DsFTTn al2looztv;gva2 iTnpoid np aane i Z a ns aua2oleq ua i iajeiapuod inaual i i i ii i mnTpos 51 ap a9efLqipm np tnIaa quamaizexa isa (fe2ua aeelqzagm ap splod np Z S6 = FIIFanDao spFod) lTal ap -FqeT B aeqoas a auexgql B <auazuaq -oaolqouom ne aSeAel seade aptios np aZnoaaejuT aaloads el anb ' anbTqdeo2olemoaqo asKleue,l saidu,p BItT! alt suep sa2ail siTnpoid ap uoitauedde sed e,u It, 1nb ' 0 : ajIaa 'uoTeal[lT; la quamassTpto.zal saide 'tauuoTOeza naTITm a9 'xnaze2 iuamafelap unone suoaiesqou snou '0DoO6Z sainaq OL luepuad quamamlpz saidy nea e a.&na aun s a-TIai isa zuela2lTai np a-lios el:a - azz altnsue qsa alozp lueanoa aq 'uoTIeITSe le aqozep a2eXeuIq snos (DoO6Z) xnlja B aalod Isa assem B-mnTpos ap alesIqigm ap S Zú e Iga ap a 0091 azeld uo 'gaozep inaozapuT unp la ueaaTa9a un,p 'gaATe;o uoTieleTS aun,p Tunm inazesai un suea s azasaxa Ànvalqeq al ans salodaz quos slellnsai s9l g (b) Same as (a) except that the mineral oil contains 1000 ppm octabromobiphenyl. * aeSua aTinq, pa! Tquenb el e auamei 'ainmolq ap amaoj snos amoiq ap mdd 9t9 ap uotaetTsTp ap npflsa al suep a2esoa (*) ageSnua alTitnqp gqTzuenb el e auamei ainiolqz ap auWoj snos aiolqz ap mdd 08g ap uoFIelltsip ap nptsgaal suep a2eso ( ) S ti mdd l> ie ZNOHI Z () aluqdIqomoaqozDoop t mdd 0001 + alveiaum alTnH i mdd If> iNOHO% i () salolqa 9 ai ap i ;; mdd 0001 + alaeaUTm alTnH i i t tiWiCWXai 0 i i d i t i t i t i t i t i t i t i t i t t t t t t t t t t t t o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o oo oo oo oo oo oo oo oo oo oo oo oo (9); j ap mdd 0001 + 001 úR i i i i i i mdd ú i ROHD (zH) 'i i m m m>>>>> au au au au au au au au; i mdd Sl>; MoúD Z ç'0 i -lXzuaqoaotlqouom ap uamoj; mdd ç i H H Z Z Z Z Z Z iz iz iz iz iz iz iz iz iz iz iz iz iz iz iz iz iz iz iz iz iz iz 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 quamaizexa isa (fe2ua aeelqzagm ap splod np Z S6 = FIIFanDao spFod) lTal ap-FqeT B aeqoas has auxgql B <auazuaq -oaolqouom does not have seade aptios np aZnoaaejuT aaloads el anb 'anbTqdeo2olemoaqo asKleue, l saidu, p BItT! alt suep sa2ail siTnpoid ap uoitaued of sed e, u It, 1nb '0: ajIaa' uoTeal [lT; the quamassTpto.zal saide 'tauuoTOeza naTITm a9' xnaze2 iuamafelap unone suoaiesqou oooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooh the aqozep a2eXeuIq snos (DoO6Z) xnlja B aalod Isa assem B-mn Appointed to the Head of the Iga ap a 0091 azeld uo 'gaozep inaozapuT unp the ueaaTa9a a, paGaATe o uoTieleTS aun, p Tunm inazesai a suea s azasaxa Invalveq al ans salodaz quos slellnsai s9l g
Claims (8)
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8712248A FR2620055B1 (en) | 1987-09-03 | 1987-09-03 | CHEMICAL PROCESS OF DESTRUCTION OF HALOGENATED ORGANIC PRODUCTS |
| CA000575896A CA1336981C (en) | 1987-09-03 | 1988-08-23 | Chemical destruction process for halogenated organic compounds |
| AT88402176T ATE85229T1 (en) | 1987-09-03 | 1988-08-29 | CHEMICAL PROCESS FOR DESTROYING HALOGENATED ORGANIC PRODUCTS. |
| DE8888402176T DE3878098T2 (en) | 1987-09-03 | 1988-08-29 | CHEMICAL METHOD FOR THE DESTRUCTION OF HALOGENATED ORGANIC PRODUCTS. |
| ES88402176T ES2053784T3 (en) | 1987-09-03 | 1988-08-29 | CHEMICAL PROCEDURE FOR THE DESTRUCTION OF HALOGENATED ORGANIC PRODUCTS. |
| EP88402176A EP0306398B1 (en) | 1987-09-03 | 1988-08-29 | Chemical process for the destruction of halogenated organic products |
| JP63219600A JPH0667409B2 (en) | 1987-09-03 | 1988-09-01 | Chemical methods for degrading halogenated organics |
| NO883893A NO176749C (en) | 1987-09-03 | 1988-09-01 | Method of Destruction of Halogenated Aryl Products |
| FI884055A FI97276C (en) | 1987-09-03 | 1988-09-02 | Process for destruction of halogenated aryl products |
| PT88421A PT88421B (en) | 1987-09-03 | 1988-09-02 | CHEMICAL PROCESS OF DESTRUCTION OF HALOGENATED ORGANIC PRODUCTS |
| IE267088A IE63083B1 (en) | 1987-09-03 | 1988-09-02 | Chemical process for destroying halogenated organic products |
| DK488488A DK169377B1 (en) | 1987-09-03 | 1988-09-02 | Process for Destruction of Halogenated Aryl Compounds |
| CN88106409A CN1016142B (en) | 1987-09-03 | 1988-09-03 | Chemical process for destroying halogenated organic products |
| KR1019880011407A KR910000196B1 (en) | 1987-09-03 | 1988-09-03 | Decomposing method for halogenated organic compound |
| US07/713,585 US5220109A (en) | 1987-09-03 | 1991-06-11 | Destruction of halogenated organic species |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8712248A FR2620055B1 (en) | 1987-09-03 | 1987-09-03 | CHEMICAL PROCESS OF DESTRUCTION OF HALOGENATED ORGANIC PRODUCTS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2620055A1 true FR2620055A1 (en) | 1989-03-10 |
| FR2620055B1 FR2620055B1 (en) | 1991-05-10 |
Family
ID=9354601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8712248A Expired - Lifetime FR2620055B1 (en) | 1987-09-03 | 1987-09-03 | CHEMICAL PROCESS OF DESTRUCTION OF HALOGENATED ORGANIC PRODUCTS |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0306398B1 (en) |
| JP (1) | JPH0667409B2 (en) |
| KR (1) | KR910000196B1 (en) |
| CN (1) | CN1016142B (en) |
| AT (1) | ATE85229T1 (en) |
| CA (1) | CA1336981C (en) |
| DE (1) | DE3878098T2 (en) |
| DK (1) | DK169377B1 (en) |
| ES (1) | ES2053784T3 (en) |
| FI (1) | FI97276C (en) |
| FR (1) | FR2620055B1 (en) |
| IE (1) | IE63083B1 (en) |
| NO (1) | NO176749C (en) |
| PT (1) | PT88421B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2656603B1 (en) | 1989-12-28 | 1993-05-21 | Atochem | METHODS OF SYNTHESIS OF BENZYLTOLUENE AND LOW CHLORINE DIBENZYLTOLUENE. |
| US5490919A (en) * | 1990-08-14 | 1996-02-13 | State Of Isreal, Atomic Energy Commission | Process for the dehalogenation of organic compounds |
| US5093011A (en) * | 1990-12-12 | 1992-03-03 | Chemical Waste Management, Inc. | Process for dehalogenation of contaminated waste materials |
| JPH04253875A (en) * | 1991-02-01 | 1992-09-09 | Chiyoda Kohan Kk | Decomposition and removal of chlorinated compound |
| DE4109639C2 (en) * | 1991-03-23 | 1994-06-01 | Metallgesellschaft Ag | Process for the decomposition of polyhalogenated organo compounds |
| JP2638483B2 (en) * | 1994-06-30 | 1997-08-06 | 株式会社関西テック | Method for treating polychlorinated aromatic compounds |
| ES2297829T3 (en) | 1994-09-30 | 2008-05-01 | Arkema France | USE FOR DISTRIBUTION TRANSFORMERS OF A POLYARILALCAN BASED DIELECTRIC COMPOSITION WITH IMPROVED DIELECTRIC PROPERTIES. |
| JP4537539B2 (en) * | 2000-06-20 | 2010-09-01 | 利夫 半谷 | Decomposition treatment method and treatment equipment for hazardous substances |
| JP2003001220A (en) * | 2001-06-25 | 2003-01-07 | Kansai Electric Power Co Inc:The | Method for separating polychlorinated aromatic compound from contaminated material |
| KR101953201B1 (en) | 2011-09-06 | 2019-02-28 | 브리티시 아메리칸 토바코 (인베스트먼츠) 리미티드 | Heating smokeable material |
| GB201217067D0 (en) | 2012-09-25 | 2012-11-07 | British American Tobacco Co | Heating smokable material |
| GB201311620D0 (en) | 2013-06-28 | 2013-08-14 | British American Tobacco Co | Devices Comprising a Heat Source Material and Activation Chambers for the Same |
| GB201500582D0 (en) | 2015-01-14 | 2015-02-25 | British American Tobacco Co | Apparatus for heating or cooling a material contained therein |
| US11924930B2 (en) | 2015-08-31 | 2024-03-05 | Nicoventures Trading Limited | Article for use with apparatus for heating smokable material |
| US20170055584A1 (en) | 2015-08-31 | 2017-03-02 | British American Tobacco (Investments) Limited | Article for use with apparatus for heating smokable material |
| US20170055575A1 (en) | 2015-08-31 | 2017-03-02 | British American Tobacco (Investments) Limited | Material for use with apparatus for heating smokable material |
| US20170119046A1 (en) | 2015-10-30 | 2017-05-04 | British American Tobacco (Investments) Limited | Apparatus for Heating Smokable Material |
| US20170119047A1 (en) | 2015-10-30 | 2017-05-04 | British American Tobacco (Investments) Limited | Article for Use with Apparatus for Heating Smokable Material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0021294A1 (en) * | 1979-06-15 | 1981-01-07 | Vertac Chemical Corporation | Chemical detoxification of toxic chlorinated aromatic compounds |
| EP0118858A1 (en) * | 1983-03-10 | 1984-09-19 | SEA MARCONI DECONTAMINATION S.r.l. | Process for the decomposition and decontamination of organic substances and halogenated toxic materials |
| US4574013A (en) * | 1985-04-18 | 1986-03-04 | Galson Research Corporation | Method for decontaminating soil |
| EP0225849A1 (en) * | 1985-12-06 | 1987-06-16 | Ciba-Geigy Ag | Process for dehalogenating halogenated aliphatic and aromatic compounds |
| EP0250748A1 (en) * | 1986-06-25 | 1988-01-07 | Hüls Aktiengesellschaft | Process for the dehalogenation of hydrocarbon oils |
-
1987
- 1987-09-03 FR FR8712248A patent/FR2620055B1/en not_active Expired - Lifetime
-
1988
- 1988-08-23 CA CA000575896A patent/CA1336981C/en not_active Expired - Lifetime
- 1988-08-29 EP EP88402176A patent/EP0306398B1/en not_active Expired - Lifetime
- 1988-08-29 AT AT88402176T patent/ATE85229T1/en not_active IP Right Cessation
- 1988-08-29 DE DE8888402176T patent/DE3878098T2/en not_active Expired - Lifetime
- 1988-08-29 ES ES88402176T patent/ES2053784T3/en not_active Expired - Lifetime
- 1988-09-01 JP JP63219600A patent/JPH0667409B2/en not_active Expired - Lifetime
- 1988-09-01 NO NO883893A patent/NO176749C/en not_active IP Right Cessation
- 1988-09-02 IE IE267088A patent/IE63083B1/en not_active IP Right Cessation
- 1988-09-02 FI FI884055A patent/FI97276C/en not_active IP Right Cessation
- 1988-09-02 DK DK488488A patent/DK169377B1/en not_active IP Right Cessation
- 1988-09-02 PT PT88421A patent/PT88421B/en not_active IP Right Cessation
- 1988-09-03 KR KR1019880011407A patent/KR910000196B1/en not_active IP Right Cessation
- 1988-09-03 CN CN88106409A patent/CN1016142B/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0021294A1 (en) * | 1979-06-15 | 1981-01-07 | Vertac Chemical Corporation | Chemical detoxification of toxic chlorinated aromatic compounds |
| EP0118858A1 (en) * | 1983-03-10 | 1984-09-19 | SEA MARCONI DECONTAMINATION S.r.l. | Process for the decomposition and decontamination of organic substances and halogenated toxic materials |
| US4574013A (en) * | 1985-04-18 | 1986-03-04 | Galson Research Corporation | Method for decontaminating soil |
| EP0225849A1 (en) * | 1985-12-06 | 1987-06-16 | Ciba-Geigy Ag | Process for dehalogenating halogenated aliphatic and aromatic compounds |
| EP0250748A1 (en) * | 1986-06-25 | 1988-01-07 | Hüls Aktiengesellschaft | Process for the dehalogenation of hydrocarbon oils |
Non-Patent Citations (1)
| Title |
|---|
| THE JOURNAL OF ORGANIC CHEMISTRY, vol. 44, no. 26, 21 décembre 1979, pages 4979-4981, American Chemical Society, Easton, PA., US; B.V.LAP et al.: "Sodium-ethanol: A superior reagent for the reductive dehalogenation of polychlorinated alicyclic molecules" * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0667409B2 (en) | 1994-08-31 |
| FI884055A (en) | 1989-03-04 |
| NO176749B (en) | 1995-02-13 |
| PT88421B (en) | 1992-10-30 |
| NO883893L (en) | 1989-03-06 |
| CN1032109A (en) | 1989-04-05 |
| KR890004780A (en) | 1989-05-09 |
| PT88421A (en) | 1989-07-31 |
| NO883893D0 (en) | 1988-09-01 |
| DE3878098D1 (en) | 1993-03-18 |
| DK169377B1 (en) | 1994-10-17 |
| IE882670L (en) | 1989-03-03 |
| CA1336981C (en) | 1995-09-12 |
| ATE85229T1 (en) | 1993-02-15 |
| ES2053784T3 (en) | 1994-08-01 |
| DE3878098T2 (en) | 1993-06-09 |
| IE63083B1 (en) | 1995-03-22 |
| NO176749C (en) | 1995-05-24 |
| FR2620055B1 (en) | 1991-05-10 |
| EP0306398B1 (en) | 1993-02-03 |
| DK488488D0 (en) | 1988-09-02 |
| KR910000196B1 (en) | 1991-01-23 |
| FI884055A0 (en) | 1988-09-02 |
| EP0306398A1 (en) | 1989-03-08 |
| JPS6470084A (en) | 1989-03-15 |
| DK488488A (en) | 1989-03-04 |
| FI97276C (en) | 1996-11-25 |
| CN1016142B (en) | 1992-04-08 |
| FI97276B (en) | 1996-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FR2620055A1 (en) | CHEMICAL METHOD FOR DESTRUCTION OF HALOGENIC ORGANIC PRODUCTS | |
| US4477354A (en) | Destruction of polychlorinated biphenyls during solvent distillation | |
| FR2598089A1 (en) | PROCESS FOR THE DECOMPOSITION OF HALOGENIC ORGANIC COMPOUNDS APPLICABLE IN PARTICULAR TO MINERAL OILS | |
| FR2643062A1 (en) | PROCESSES FOR EXTRACTING, RECOVERING OR REMOVING NITROPHENOLIC BY-PRODUCTS FROM WASTEWATER NITRATION WATER | |
| EP0446086B1 (en) | Composition comprising methyl and benzyl derivatives of diphenylmethane and its use as dielectricum | |
| EP0435737B1 (en) | Process for the synthesis of benzyltoluene and dibenzyltoluene with low chlorine content | |
| EP0197869B1 (en) | Process for the preparation of pentafluoroethoxy- and pentafluoroethyl thiobenzene derivatives | |
| JP4084073B2 (en) | Detoxification method for organic halogen compounds | |
| JP2002212109A (en) | Method for treating organic halide compound | |
| CA1301194C (en) | Process for selective chloration of phenolic compounds | |
| US5616821A (en) | Methods for purifying and recovering contaminated refrigerants with solutions of bases in organic solvents | |
| JP3935758B2 (en) | Detoxification treatment method and detoxification treatment system for organic halogen compounds | |
| BE903383A (en) | Eliminating poly:chloro:bi:phenyl or prods. from electrical appts. - using chlorinated and/or fluorinated ethane deriv. pref. with a liquid aliphatic hydrocarbon | |
| BE1003331A3 (en) | Breakdown method for halogenated organic compound | |
| JPS629160B2 (en) | ||
| EP0130876A1 (en) | Process for the simultaneous halogenation and fluorination of aromatic compounds | |
| EP0172761B1 (en) | Process for the preparation of pure hydrates of fluoral and hexafluoroacetone from hemiacetals | |
| FR2810317A1 (en) | Separating hydroxybenzonitrile compounds used as dyes or agrochemical intermediates from gaseous reaction mixture by physical or chemical treatment | |
| JP2000246002A (en) | Method for cleaning solid material contaminated with organic halide and device therefor | |
| FR2739376A1 (en) | PROCESS FOR THE PREPARATION OF 2-CHLORO-4-METHYLPHENOL FROM 4-METHYLPHENOL | |
| JP2004073312A (en) | Method and apparatus for decomposition treatment of organic halide | |
| EP0422986B1 (en) | Process for the preparation of dielectric fluids | |
| JP4028225B2 (en) | Method for decomposing halogenated organic compounds in solids | |
| JPH0825913B2 (en) | Method for treating polychlorinated aromatic compounds | |
| JP3104323B2 (en) | How to remove thiophosgene |